CN110416630B - All-solid-state battery - Google Patents

All-solid-state battery Download PDF

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CN110416630B
CN110416630B CN201910333307.6A CN201910333307A CN110416630B CN 110416630 B CN110416630 B CN 110416630B CN 201910333307 A CN201910333307 A CN 201910333307A CN 110416630 B CN110416630 B CN 110416630B
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positive electrode
active material
negative electrode
solid
dense
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CN110416630A (en
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濑上正晴
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Toyota Motor Corp
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Toyota Motor Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties

Abstract

The present invention relates to an all-solid battery. The separator layer of the all-solid battery disclosed herein has a protruding portion protruding outward beyond the end of the facing portion between the positive electrode and the negative electrode, and at least a part of the protruding portion is formed of a dense structure to such an extent as to prevent the positive electrode and the negative electrode from coming into contact with each other. Here, when a shortest distance from an end of an opposing portion between the positive electrode and the negative electrode to the dense-structure portion is represented by a, and a shortest distance from a surface of the negative electrode active material layer at the end of the opposing portion between the positive electrode and the negative electrode to the positive electrode current collector at the end of the opposing portion is represented by B, the dense-structure portion is formed at a position having a < B.

Description

All-solid-state battery
Cross Reference to Related Applications
The present application claims priority based on japanese patent application No. 2018-086171, filed on 27/4/2018, the entire contents of which are incorporated by reference in the present specification.
Technical Field
The present invention relates to an all-solid-state battery provided with a solid electrolyte. And particularly to the construction of the separator layer of an all-solid battery.
Background
Secondary batteries such as lithium ion secondary batteries that can realize relatively high output and high capacity are important as power sources mounted on vehicles using electricity as a driving source, or power sources mounted on electric products such as personal computers and mobile phone terminals. In particular, a lithium ion secondary battery that is lightweight and can obtain a high energy density is preferable as a high output power source for driving vehicles such as Electric Vehicles (EV), plug-in hybrid vehicles (PHV), and Hybrid Vehicles (HV), and the demand is expected to expand in the future.
As one embodiment of the high-output secondary battery, a battery using a powdery solid electrolyte instead of a liquid electrolyte (electrolytic solution), that is, a secondary battery in an all-solid battery form, is cited.
Since the all-solid battery does not use a liquid electrolyte, it is not necessary to perform a complicated process in the case of handling an organic solvent such as a nonaqueous electrolytic solution, and a laminated electrode body having a laminated structure including positive and negative electrodes and a separator layer (also referred to as a solid electrolyte layer) can be easily constructed. In addition, since no electrolyte is used, the structure of the electrode body is simplified, and the battery capacity per unit volume of the battery can be improved. This is expected as a high-output power source for driving vehicles, which is required to have a higher capacity.
As one embodiment of the all-solid battery, there is an all-solid battery including a separator layer (solid electrolyte layer) having solid electrolyte particles and a porous substrate made of a polymer such as polyolefin. For example, JP2017-183111a describes a separator in which a layer of crystalline oxide-based inorganic solid electrolyte particles having an average particle diameter of 5 μm to 100 μm is held on a porous substrate made of a polyolefin-based resin or the like. Such a separator having a porous substrate has the following advantages: this contributes to improvement in ion conductivity by making the separator layer thin, and also contributes to improvement in workability of the battery by improving flexibility of the separator layer.
Disclosure of Invention
However, the laminated electrode body including the separator in which the solid electrolyte particles are held on the porous substrate as described in patent document 1 has the following problems.
That is, in such a laminated electrode body, in order to secure stable charge and discharge, the size of the negative electrode is generally increased as compared with the positive electrode. Therefore, the negative electrode has a protruding portion protruding outward beyond the positive-negative electrode opposing portion (positive-negative electrode laminated portion).
In order to more reliably prevent short-circuiting, the separator layer is formed to have a size equal to or larger than that of the negative electrode. Therefore, the separator layer also has a protruding portion protruding outward from the opposing portion of the positive and negative electrodes. Here, the projecting portion projects from the positive-negative electrode opposing portion of the laminated electrode body, and therefore, the pressure applied in the laminating direction is not applied so strongly. Thus, at the protruding portion, the solid electrolytic particles tend to easily fall off from the porous base material upon application of some impact or the like. The falling off of the solid electrolyte particles at the protruding portion, particularly the falling off of the solid electrolyte particles from the portion facing the negative electrode protruding portion, is not preferable because it can be a factor of causing a short circuit by the negative electrode protruding portion, which easily moves at the end portion of the laminated electrode body, coming into contact with the positive electrode end portion.
The present invention has been made to solve the above-described problems associated with an all-solid-state battery including a separator layer obtained by holding the solid electrolyte particles on a porous substrate, and an object of the present invention is to provide an all-solid-state battery including a separator layer that holds the solid electrolyte particles in a porous substrate and has a structure capable of reliably preventing a protruding portion of a negative electrode from coming into contact with an end portion of a positive electrode.
In order to achieve the above object, an all-solid battery disclosed herein is an all-solid battery including a laminated electrode body having a laminated structure, the laminated electrode body having: a positive electrode in which a positive electrode active material layer containing positive electrode active material particles and solid electrolyte particles is formed on a positive electrode current collector; an anode in which an anode active material layer containing anode active material particles and solid electrolyte particles is formed on an anode current collector; and a separator layer comprising a substrate having a porous structure (hereinafter also simply referred to as "porous substrate") and solid electrolyte particles held in the substrate.
In the all-solid-state battery disclosed herein, the negative electrode and the separator layer each have a protruding portion protruding outward beyond an end portion of an opposing portion between the positive electrode and the negative electrode in at least a part of an end portion of the laminated electrode body.
At least a part of the protruding portion of the separator layer is formed to such an extent that the contact between the positive electrode and the negative electrode is prevented by a dense structure.
When a shortest distance from an end of the facing portion of the positive electrode and the negative electrode to the dense-structure portion is defined as a and a shortest distance from a surface of the negative electrode active material layer at the end of the facing portion of the positive electrode and the negative electrode to the positive electrode current collector at the end of the facing portion is defined as B, the dense-structure portion is formed at a position where a < B is provided.
The present inventors have initiated that at least the protruding portion of the separator layer, which is opposed to a portion of the protruding portion of the negative electrode that may come into contact with the end portion of the positive electrode, is formed of the above-described dense structure portion in order to prevent the occurrence of defects accompanying the falling-off of solid electrolyte particles at the protruding portion of the separator layer in advance, and finally completed the present invention.
That is, in the all-solid battery disclosed herein, as described above, the dense structural portion is provided in the protruding portion of the separator layer in such a manner as to satisfy a < B. This structure has the following configuration: even in the case where the protruding portion of the negative electrode moves to a position close to the end of the opposite positive electrode when some external force is applied, a situation in which defects are generated following the falling-off of the solid electrolyte particles does not occur at all, so that the contact of the protruding portion of the negative electrode with the end of the positive electrode (more specifically, the positive electrode current collector exposed at the end) can be reliably prevented.
In a preferred embodiment of the all-solid battery disclosed herein, the porous substrate and the dense structure portion are each made of a thermoplastic resin.
A thermoplastic resin is preferable as a polymer material forming the porous base material, and further, a part of the porous structure can be easily made into a heat-fused body by heating to become a dense structure. In addition, insulation suitable as a separator base material can also be achieved.
Porous substrates having a porosity (e.g., as measured by archimedes' method) of at least 80% are preferred. The porous substrate having a high porosity can hold solid electrolyte particles at a higher ratio, and can realize high ion conductivity in the separator layer.
In a preferred embodiment of the all-solid-state battery disclosed herein, the laminated electrode body is formed by laminating rectangular positive and negative electrodes and a separator layer. Further, the dense structure portion is formed in an extension portion of an end portion of each edge of the rectangular separator layer.
In the all-solid-state battery having this configuration, the above-described short circuit prevention can be achieved at any edge end portion in the laminated electrode body formed by laminating the rectangular positive and negative electrodes and the separator layer.
Drawings
Fig. 1 is a diagram schematically illustrating the structure of an all-solid-state battery including laminated electrode bodies.
Fig. 2 is a view schematically illustrating an end portion of a laminated electrode body including a porous base material in a separator layer, and schematically illustrates a state before the end portion of the base material is heat-welded.
Fig. 3 is a view schematically illustrating an end portion of a laminated electrode body including a porous base material in a separator layer, and is a view schematically illustrating a state after the end portion of the base material is thermally welded to form a dense structure portion.
Fig. 4 is a view schematically illustrating a state in which the protruding portion of the negative electrode is prevented from contacting the positive electrode by the dense structure portion of the separator layer.
Fig. 5 is a diagram schematically illustrating a configuration in which the dense structure portion is formed at a position having a < B.
Detailed Description
Hereinafter, preferred embodiments of the all-solid battery disclosed herein will be described with reference to the drawings as appropriate. It should be noted that matters necessary for implementing the present invention other than the matters specifically mentioned in the present specification can be grasped as design matters by those skilled in the art based on the prior art in the field. The numerical ranges a to B (A, B is an arbitrary number) in the present specification represent a to B.
In the present specification, the term "(positive and negative electrode) active material" means a material that participates in the absorption and release of charge carriers (for example, lithium ions in a lithium ion secondary battery) on the positive electrode side or the negative electrode side.
In the following description, an all-solid-state lithium-ion secondary battery is exemplified as an application target of the technology disclosed herein, but the technology is not limited thereto. As the type of all-solid-state battery disclosed herein, other metal ions may be used as charge carriers, and all-solid-state batteries constituting, for example, a sodium ion secondary battery, a magnesium ion secondary battery, and the like may be used.
In fig. 1, an all-solid battery (here, an all-solid lithium ion secondary battery) 1 provided with a laminated electrode body 10 of a typical laminated structure is schematically shown. That is, roughly speaking, the all-solid lithium ion secondary battery 1 according to the present embodiment is a battery configured by housing a laminated electrode assembly 10 in a predetermined housing (battery case), not shown, the laminated electrode assembly 10 being configured by laminating a predetermined number of sheet-shaped positive electrodes 20 and negative electrodes 40 with separator layers (solid electrolyte layers) 30 interposed therebetween.
As the frame body, a metal (for example, aluminum) frame body can be preferably used from the viewpoint of high physical strength, heat dissipation, and the like. Alternatively, the battery module may be formed of a laminate film in view of mountability and weight reduction of the entire battery module. A preferable example in this case is a laminated film having a three-layer structure in which a metal layer such as aluminum is disposed between 2 synthetic resin layers.
As shown in the drawing, the positive electrode 20 is provided with a positive electrode current collector 22 formed of aluminum foil or the like, and positive electrode active material layers 24 formed on both surfaces thereof and containing a predetermined positive electrode active material and a solid electrolyte. The negative electrode 40 includes a negative electrode current collector 42 formed of a copper foil or the like, and a negative electrode active material layer 44 formed on both surfaces thereof and containing a predetermined negative electrode active material and a solid electrolyte.
The separator layer 30 is a layer containing solid electrolyte particles of the same type as the solid electrolyte contained in the positive and negative electrode active material layers 24 and 44 and a porous substrate described later, and functions as a separator for insulating the positive and negative electrodes from each other while ensuring ion conductivity. Next, each layer constituting the laminated electrode assembly 10 will be described in detail.
The positive electrode 20 provided in the all-solid-state lithium-ion secondary battery 1 according to the present embodiment is not particularly limited, and any positive electrode used in such a battery may be used.
The positive electrode collector 22 may be used without particular limitation as a positive electrode collector for such a battery. Typically, the positive electrode collector made of metal having good conductivity is preferably made of a metal material such as aluminum, nickel, titanium, or stainless steel. Aluminum (e.g., aluminum foil) is particularly preferred. The thickness of the positive electrode collector 22 is not particularly limited, but is preferably about 5 to 50 μm, and more preferably about 8 to 30 μm, from the viewpoint of satisfying both the capacity density of the battery and the strength of the collector.
The positive electrode active material layer 24 is a layer containing a positive electrode active material and a solid electrolyte, and may further contain a conductive material and a binder (binder) as needed.
As the solid electrolyte that can be used, various oxide-based solid electrolytes or sulfide-based solid electrolytes can be cited. Preferable examples of the oxide-based solid electrolyte include various oxides having a NASICON structure, a garnet structure, or a perovskite structure.
Examples thereof include compounds represented by the general formula: li x AO y (where A is B, C, Al, Si, P, S, Ti, Zr, Nb, Mo, Ta or W, and x and y are positive real numbers). As a specific example, Li is cited 3 BO 3 、LiBO 2 、Li 2 CO 3 、LiAlO 2 、Li 4 SiO 4 、Li 2 SiO 3 、Li 3 PO 4 、Li 2 SO 4 、Li 2 TiO 3 、Li 4 Ti 5 O 12 、Li 2 Ti 2 O 5 、Li 2 ZrO 3 、LiNbO 3 、Li 2 MoO 4 、Li 2 WO 4 And the like. Alternatively, Li is preferably used 2 O-B 2 O 3 -P 2 O 5 Series, Li 2 O-SiO 2 Series, Li 2 O-B 2 O 3 Series, Li 2 O-B 2 O 3 -ZnO-based glass or glass-ceramic.
In particular, a sulfide-based solid electrolyte is preferably used from the viewpoint of having high ion conductivity. Examples thereof include Li 2 S-SiS 2 Series, Li 2 S-P 2 S 3 Series, Li 2 S-P 2 S 5 Series, Li 2 S-GeS 2 Series, Li 2 S-B 2 S 3 Series, Li 3 PO 4 -P 2 S 5 Series, Li 4 SiO 4 -Li 2 S-SiS 2 Such as glass or glass-ceramic.
In addition, from the viewpoint of achieving higher ion conductivity, it is preferable to use Li 2 Li-based compositions of S and lithium halides (e.g. LiCl, LiBr, LiI) 2 A solid solution of S. Preferred examples thereof include LiBr-Li 2 S-P 2 S 5 、LiI-Li 2 S-P 2 S 5 、LiBr-LiI-Li 2 S-P 2 S 5 And the like.
Average particle diameter (D) of solid electrolyte particles used, obtained by laser diffraction/scattering method 50 ) For example, about 0.5 μm to 10 μm is suitable, and about 1 μm to 5 μm is particularly preferable.
As the positive electrode active material contained in the positive electrode active material layer 24, various compounds conventionally used in such batteries can be used. Preferable examples include LiCoO 2 、LiNiO 2 、LiNi x Co y Mn (1-x-y) O 2 (here, 0 < x < 1, 0 < y < 1, 0 < x + y < 1), and the like. Alternatively, Li may be cited 2 NiMn 3 O 8 、LiMn 2 O 4 、Li 1+x Mn 2-y M y O 4 (where M is a spinel-structured composite oxide represented by 0. ltoreq. x < 1, 0. ltoreq. y < 2), or one or more metal elements selected from Al, Mg, Co, Fe, Ni and Zn; LiFePO 4 And other olivine-structured complex compounds.
Average particle diameter (D) obtained by laser diffraction/scattering method for positive electrode active material 50 ) For example, about 0.5 μm to 20 μm is suitable, and about 1 μm to 10 μm is particularly preferable.
As particularly preferable positive electrode active materials, there can be mentioned: the positive electrode active material is in a form in which at least a part of the surface of the active material particles is covered with a coating film formed of a solid electrolyte. In particular, it is preferable to use a positive electrode active material coated with an oxide-based solid electrolyte. By using the positive electrode active material particles coated with the solid electrolyte, the positive electrode active material in the positive electrode active material layer 24 can be more favorably adhered to the solid electrolyte.
The thickness of the solid electrolyte membrane covering the positive electrode active material particles is not particularly limited, but is preferably not so thick as to significantly hinder the electrical conductivity. For example, the average film thickness is preferably 0.1nm to 100 nm. The coating rate of the solid electrolyte membrane in the surface area of the positive electrode active material particles is preferably 30% or more, and more preferably 40% or more.
The compounding ratio of the positive electrode active material to the solid electrolyte in the positive electrode active material layer 24 is not particularly limited. Typically, the mass ratio (P: S) of the positive electrode active material (P) to the solid electrolyte (S) may be about 50: 50 to 95: 5.
The thickness of the positive electrode active material layer 24 is not particularly limited. Typically, it may be 10 μm to 500. mu.m.
The positive electrode active material layer 24 may contain various optional components in addition to the positive electrode active material and the solid electrolyte, as in the positive electrode active material layer of the conventional battery. For example, conductive materials, adhesives, and the like may be included. As the conductive material, carbon black such as acetylene black or other (graphite, carbon nanotube, etc.) carbon materials can be preferably used. As the binder, a fluorine-based binder such as polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE), or a rubber-based binder such as Styrene Butadiene Rubber (SBR) can be preferably used.
The negative electrode 40 provided in the all-solid-state lithium-ion secondary battery 1 according to the present embodiment is not particularly limited, and a negative electrode used in such a battery can be used.
The anode current collector 42 may use, without particular limitation, an anode current collector used as an anode current collector of such a battery. Typically, a metal negative electrode current collector having good conductivity is preferable, and for example, copper (e.g., copper foil) or an alloy mainly composed of copper can be used. The thickness of the negative electrode current collector 42 is not particularly limited, but is preferably about 5 to 50 μm, more preferably about 8 to 30 μm, from the viewpoint of satisfying both the capacity density of the battery and the strength of the current collector.
The negative electrode active material layer 44 is a layer containing a negative electrode active material and a solid electrolyte, and may further contain a binder or the like as needed.
The solid electrolyte contained in the negative electrode active material layer 44 may be the same as that contained in the positive electrode active material layer 24, and redundant description is omitted.
As the negative electrode active material contained in the negative electrode active material layer 24, various compounds conventionally used in such batteries can be used. For example, carbon-based negative electrode active materials such as graphite, mesocarbon microbeads, and carbon black (acetylene black, ketjen black, etc.) can be cited as examples.
In addition, as the negative electrode active material having a high energy density, a negative electrode active material containing silicon (Si) or tin (Sn) as a constituent element can be cited.
Specifically, examples of the Si (silicon) -based negative electrode active material include Si and SiO a Silicon oxide expressed by (0.05 < a < 1.95 here), SiC b Silicon carbide represented by (0 < b < 1), SiN c Silicon nitride represented by (0 < c < 4/3), and the like.
As another example of the silicon-based negative electrode active material, an alloy material containing silicon and an element other than silicon is cited. Examples of the element other than silicon include Fe, Co, Sb, Bi, Pb, Ni, Cu, Zn, Ge, In, Sn, and Ti.
On the other hand, examples of the Sn-based negative electrode active material include tin, tin oxide, tin nitride, tin-containing alloy, and solid solutions thereof. Part of the tin atoms contained in these may be replaced with 1 or 2 or more elements.
Examples of the oxide include SnO d Tin oxide and tin dioxide (SnO) represented by (0 < d < 2) 2 ) And so on. Examples of the tin-containing alloy include a Ni-Sn alloy, a Mg-Sn alloy, a Fe-Sn alloy, a Cu-Sn alloy, and a Ti-Sn alloy. As the tin compound, SnSiO 3 、Ni 2 Sn 4 、Mg 2 Sn, and the like.
Average particle diameter (D) of negative electrode active material obtained by laser diffraction/scattering method 50 ) For example, about 1 μm to 20 μm is suitable, and about 2 μm to 10 μm is particularly preferred.
The thickness of the anode active material layer 44 is not particularly limited. Typically, it may be 10 μm to 500. mu.m.
The compounding ratio of the negative electrode active material to the solid electrolyte in the negative electrode active material layer 44 is not particularly limited. Typically, the mass ratio (N: S) of the negative electrode active material (N) to the solid electrolyte (S) may be about 50: 50 to 95: 5.
In addition to the negative electrode active material and the solid electrolyte, the negative electrode active material layer 44 may contain various optional components as in the case of the negative electrode active material layer of the conventional battery. For example, a conductive material, a binder, or the like may be contained as in the positive electrode active material layer 24. As the conductive material, carbon black such as acetylene black, and other carbon materials (such as graphite and carbon nanotube) can be preferably used. As the binder, a fluorine-based binder such as PVDF or PTFE, or a rubber-based binder such as SBR can be preferably used.
The separator layer 30 provided in the all-solid lithium ion secondary battery 1 according to the present embodiment is composed of various solid electrolyte particles 34 and a substrate 32 having a porous structure, as in the case of the conventional battery. In the separator layer 30, various optional ingredients may be included in addition to the porous substrate 32 and the solid electrolyte particles 34. For example, the binder may be included in the same manner as the positive and negative electrode active material layers, and the retention of the solid electrolyte particles 34 on the substrate 32 can be improved.
As shown in fig. 2, the porous substrate 32 is a substrate having a three-dimensional mesh structure with a porosity of preferably 80% or more, and the solid electrolyte particles 34 are held in the pores of the substrate 32. This can improve the mechanical strength while maintaining the lithium ion conductivity of the separator layer 30. The porosity can be determined by the Archimedes method. Alternatively, the volume (cm) of the substrate may be sized 3 ) And mass (g) and true density (g/cm) 3 ) It is easy to obtain.
The thickness of the separator layer 30 is not particularly limited. About 10 μm to 200 μm is suitable in view of high lithium ion conductivity and suppression of internal resistance, and 100 μm or less is preferable.
The porous base material 32 is preferably formed of a thermoplastic resin material. For example, polyolefin resins such as polyethylene and polypropylene are preferable. Alternatively, thermoplastic resins such as polyamide, polyamideimide, thermoplastic polyimide, and thermoplastic polyester resins are also preferable. Alternatively, the substrate may be a nonwoven fabric substrate made of glass fibers or the like.
As shown in fig. 2, the porous base material 32 of the separator layer 30 according to the present embodiment is formed only of the base material 32 without holding solid electrolyte particles in the protruding portion 33 protruding outward from the positive and negative electrode facing portion (positive and negative electrode laminated portion).
As shown in fig. 3, the extension portion 33 is thermally welded at an appropriate heating temperature corresponding to the type of thermoplastic resin, and the three-dimensional mesh structure is eliminated in advance to form a dense structure portion 33A having a dense structure.
As a result, as shown in fig. 4, even when vibration or other external force is applied to the laminated electrode body 10 in the frame 50 formed of an aluminum laminated film or the like to bring the protruding portion 41 of the negative electrode 40 close to the end of the facing positive electrode 20 (positive electrode collector 22), the dense structure portion 33A becomes a space, and contact between the positive electrode and the negative electrode is prevented, and short-circuiting is prevented.
As shown in fig. 5, typically, when a shortest distance from an end of the positive-negative electrode facing portion (positive-negative electrode stacked portion) to the dense-structured portion 33A is represented by a and a shortest distance from the surface of the negative electrode active material layer 44 at the end of the positive-negative electrode facing portion to the positive electrode collector 22 at the end of the facing portion is represented by B, the dense-structured portion 33A is formed at a position having a < B. Thereby, the short-circuit prevention effect shown in fig. 4 can be reliably achieved.
The all-solid-state lithium-ion secondary battery 1 disclosed herein is not limited in its manufacturing method as long as it has the above-described configuration. Typically comprising: the method for manufacturing a battery module includes a step of forming a laminated electrode body including a positive electrode, a negative electrode, and a separator layer, a step of pressing the laminated electrode body in a lamination direction thereof, a step of housing the pressed laminated electrode body in a predetermined frame to form a battery module, and a step of primarily charging the battery module (i.e., the laminated electrode body).
For example, the formation of each of the positive electrode active material layer 24 and the negative electrode active material layer 44 can be performed by the following steps, as in the case of a conventional battery of this type: a paste (slurry) composition containing the above-described components is prepared, and the paste (slurry) composition is applied to the positive electrode collector 22 or the negative electrode collector 42, dried, and pressed under an appropriate pressure (for example, about 5MPa to 300 MPa).
In addition, the separator layer 30 may be formed by: a paste (slurry) composition containing solid electrolyte particles and other components (such as a binder) is prepared, and the paste (slurry) composition is applied to a separately prepared porous substrate and dried.
Then, the laminated electrode body 10 can be produced by laminating the positive electrode 20 on which the positive electrode active material layer 24 is formed, the negative electrode 40 on which the negative electrode active material layer 44 is formed, and the separator layer 30.
Then, the laminated electrode body 10 is pressed at a predetermined pressing pressure (for example, 2 tons/cm) 2 10 ton/cm 2 ) The pressing is performed to improve the mechanical strength of the laminated electrode body 10 and the conductivity (in other words, ion conduction path) in each layer. Then, a positive electrode terminal and a negative electrode terminal (not shown) for external connection are connected to the positive electrode 20 and the negative electrode 40 of the laminated electrode body 10, respectively, whereby a battery module can be obtained.
The target all-solid-state battery (in the present embodiment, the all-solid-state lithium ion secondary battery) 1 may be manufactured by subjecting the obtained battery module to a primary charging process and a primary discharging process, and further, if desired, subjecting the battery module to an appropriate aging process (エージング process). The first charge/discharge treatment and the aging treatment may be appropriately performed according to the purpose of use and the battery capacity, and the detailed description thereof will be omitted since the features of the present invention are not provided.
In addition, when the all-solid-state battery disclosed herein is used as a high-output power source for driving a vehicle, a plurality of all-solid-state batteries are connected to each other to construct a battery module (also referred to as a battery pack).
Hereinafter, several test examples relating to the all-solid-state battery (here, all-solid-state lithium-ion secondary battery) disclosed herein will be described, but the present invention is not intended to be limited to the all-solid-state battery shown in the test examples. The following compounding ratios are weight ratios.
[ test example 1: production of all-solid-State Battery for test
A total of 11 types of all-solid-state lithium-ion secondary batteries of samples 1 to 11 were produced by the method described below.
< sample 1 >
Preparation of a Positive electrode active Material coated with a solid electrolyte
As the positive electrode active material, the average particle diameter (D) measured by a laser diffraction/scattering method was used 50 ) LiNi of 6 μm 1/3 Mn 1/3 Co 1/3 O 2 And (3) powder. Then, the surface of the positive electrode active material was coated with LiNbO by a sol-gel method 3 。
Specifically, equimolar LiOC 2 H 5 And Nb (OC) 2 H 5 ) 5 The metal alkoxide solution was dissolved in an ethanol solvent to prepare a coating metal alkoxide solution. Then, a metal alkoxide solution for coating was applied to the surface of the positive electrode active material using a rotary flow coater (model: SFP-01, product of Powrex corporation) under atmospheric pressure. At this time, the treatment time was adjusted so that the thickness of the coating film became about 5 nm. Then, theThe coated positive electrode active material was heat-treated at 350 ℃ under atmospheric pressure for 1 hour to obtain a positive electrode active material comprising LiNbO 3 Surface-coated LiNi 1/3 Mn 1/3 Co 1/3 O 2 The positive electrode active material of (1).
Preparation of the positive electrode
Using the positive electrode active material obtained above, and as a sulfide solid electrolyte, an average particle diameter (D) measured by a laser diffraction/scattering method 50 ) 15LiBr 10LiI 75(0.75 Li) of 2.5 μm 2 S·0.25P 2 S 5 ) Glass ceramic, and a positive electrode was produced.
Specifically, the positive electrode active material layer forming composition (positive electrode paste) was obtained by weighing the positive electrode active material and the sulfide solid electrolyte at a weight ratio of active material: solid electrolyte of 75: 25, further weighing approximately 4 parts of PVDF-based binder and approximately 6 parts of conductive material (acetylene black) relative to 100 parts of the active material, blending these components in butyl butyrate so that the solid content becomes 70 wt%, and kneading the components with a mixer.
Next, the obtained positive electrode paste was uniformly applied onto a positive electrode collector made of an aluminum foil 15 μm in thickness by a doctor blade coating method using a commercially available applicator so that the weight per unit area became 25mg/cm 2 . Thereafter, the coating film was dried at 120 ℃ for approximately 3 minutes to obtain a positive electrode in which a positive electrode active material layer was formed on one surface of a positive electrode current collector made of aluminum foil.
Preparation of negative electrode
Using an average particle diameter (D) measured by a laser diffraction/scattering method 50 ) A negative electrode was produced by using Si (silicon) powder of 6 μm as a negative electrode active material and the same sulfide solid electrolyte as the positive electrode as a solid electrolyte.
Specifically, the composition for forming the negative electrode active material layer (negative electrode paste) was obtained by weighing the negative electrode active material and the sulfide solid electrolyte at a weight ratio of 55: 45, further weighing approximately 6 parts of PVDF-based binder and approximately 6 parts of conductive material (acetylene black) with respect to 100 parts of the active material, blending them in butyl butyrate so that the solid content becomes 70 wt%, and kneading the mixture with a mixer.
Next, the obtained negative electrode paste was uniformly applied onto a negative electrode collector made of a copper foil having a thickness of 15 μm by a doctor blade coating method using a commercially available applicator so that the weight per unit area became 5.6mg/cm 2 . Thereafter, the coating film was dried at 120 ℃ for approximately 3 minutes to obtain a negative electrode in which a negative electrode active material layer was formed on one surface of a negative electrode current collector made of copper foil.
Preparation of the diaphragm layer
A fibrous polyethylene film having a porosity of 85% and a thickness of 40 μm was used as a porous substrate, and a solid electrolyte layer-forming composition was applied to both surfaces of the polyethylene film.
Specifically, 98 parts of sulfide solid electrolyte and 2 parts of SBR binder were weighed and mixed in a heptane solvent so that the solid content became 70 wt%, and ultrasonic dispersion treatment was performed for approximately 2 minutes using an ultrasonic dispersion apparatus (model No. UH-50, a product of SMT), thereby obtaining a composition for forming a solid electrolyte (solid electrolyte paste).
Subsequently, the obtained solid electrolyte paste was uniformly applied to both surfaces of the polyethylene film in the same manner as in the production of the positive electrode, so that the weight per unit area per one surface was 4mg/cm 2 . Thereafter, natural drying was performed. Thereafter, the coated portions were wiped off with heptane to a coating area of 2cm × 2cm, and dried at 100 ℃ for 30 minutes. Thus, a plurality of 4cm × 4cm rectangular separator sheets were produced, each having a 2cm × 2cm solid electrolyte coated portion in the center and a 1cm or more solid electrolyte uncoated portion in the periphery.
Preparation of all-solid-state batteries
The positive electrode thus produced was punched out to 2cm × 2cm, and arranged such that the positive electrode active material layer was attached to the 2cm × 2cm solid electrolyte-coated surface of the separator sheet at 1 ton/cm 2 The pressing pressure of (a) is performed.
Then, the negative pole is punchedThe separator sheet was pressed 3cm × 3cm, and one surface of the separator sheet to which the positive electrode was not bonded was disposed at the center of the negative electrode active material layer. This formed a laminate in which the extending portions of the negative electrode and the separator sheet were formed around the positive and negative electrode facing portions (positive and negative electrode laminated portions) of 2cm × 2 cm. Then, the temperature was adjusted to 170 ℃ at 3 tons/cm in the stacking direction 2 The pressing pressure of (a) is performed. The pressing process was performed a total of 12 times. 2 of these laminates were produced, and negative electrode current collectors were laminated and stacked, and the above-described pressing was further performed 3 times, thereby producing a laminated electrode body.
Next, the extending portions of the separator sheets present in the 4 sides of the laminated electrode body were thermally welded at 180 ℃ for approximately 5 seconds by Lamisealer (ラミシーラ), to form dense-structure portions. At this time, since it was difficult to visually distinguish the numerical values (distances) between a and B, the end portions of the positive and negative electrode laminated portions were observed with an optical microscope to form a dense structure portion such that a/B became 0.8.
The laminated electrode assembly thus obtained was sealed with a frame body formed of an aluminum laminate film provided with positive and negative electrode terminals in advance, and an all-solid battery for testing (all-solid lithium ion secondary battery) of sample 1 was produced.
< sample 2 >
An all-solid-state battery for testing (all-solid lithium ion secondary battery) of sample 2 was produced by using the same materials and procedures as those of sample 1, except that the thermal welding temperature by Lamisealer was changed to 170 ℃.
< sample 3 >
An all-solid-state battery for testing (all-solid lithium-ion secondary battery) of sample 3 was produced by the same materials and steps as those of sample 1, except that the dense structural portion was formed so that a/B was 0.5.
< sample 4 >
In the production of the separator sheet, the porosity of the polyethylene film was changed to 80%, and the weight per unit area per one surface was changed to 3.8mg/cm 2 Except for this, an all-solid-state battery for testing (all-solid-state lithium-ion secondary battery) of sample 4 was produced using the same materials and steps as those of sample 1)。
< sample 5 >
In the production of a separator sheet, the porosity of the polyethylene film was changed to 90%, and the weight per unit area per one surface was changed to 4.2mg/cm 2 Otherwise, an all-solid-state battery for testing (all-solid-state lithium-ion secondary battery) of sample 5 was produced using the same materials and steps as those of sample 1.
< sample 6 >
An all-solid battery for testing (all-solid lithium ion secondary battery) of sample 6 was produced by the same materials and procedures as those of sample 1 except that a film made of polyamideimide having a porosity of 85% was used instead of the polyethylene film and the temperature of thermal welding by Lamisealer was changed to 250 ℃.
< sample 7 >
An all-solid battery for testing (all-solid lithium ion secondary battery) of sample 7 was produced by the same materials and procedures as those of sample 1 except that a film made of thermoplastic polyimide having a porosity of 85% was used instead of the polyethylene film and the temperature of thermal welding by Lamisealer was changed to 250 ℃.
< sample 8 >
An all-solid-state battery for testing (all-solid-state lithium-ion secondary battery) of sample 8 was produced using the same materials and steps as those of sample 1, except that the thermal welding treatment by Lamisealer was not performed (that is, the dense structure portion was not formed).
< sample 9 >
An all-solid-state battery for testing (all-solid lithium-ion secondary battery) of sample 9 was produced by the same materials and steps as those of sample 1, except that the solid electrolyte paste was directly applied onto the positive electrode active material layer without using a support.
< sample 10 >
An all-solid-state battery for testing (all-solid lithium-ion secondary battery) of sample 10 was produced by the same materials and procedures as sample 1, except that the temperature of the thermal welding by Lamisealer was changed to 150 ℃.
< sample 11 >
An all-solid-state battery for testing (all-solid lithium-ion secondary battery) of sample 11 was produced by the same materials and steps as those of sample 1, except that the dense structural portion was formed so that the a/B became 1.3.
[ test example 2: measurement of porosity of thermally welded part of extension part of diaphragm sheet for each sample ]
The thickness of the heat-fused portion was measured by an optical microscope, and the porosity of the heat-fused portion was calculated. The calculation results are shown in the corresponding columns of table 1.
[ test example 3: resistance measurement and vibration test of each sample
The batteries of the respective samples were charged and discharged for the first time, and then resistance measurement was performed to investigate the presence or absence of short circuit due to the vibration test.
Specifically, the batteries of the respective samples were subjected to fixed dimensional restraint (dimensional restraint) in the stacking direction of the electrode bodies at 10MPa, and then subjected to initial charge and discharge under the following conditions. That is, the charge was 4.1V-CCCV charge with a current magnification of 15mA and a current magnification of 1mA being cut off (カット), and the discharge was CC 2.5V cut off with a current magnification of 15 mA. Then, the battery resistance was calculated from the voltage drop after charging a half of the discharge capacity obtained in the initial charge-discharge and discharging at 50mA for 5 seconds. As a result, all the samples were found to have a cell resistance of 3.4 Ω to 4.6 Ω, and were not used.
As for the vibration test, charging was performed to 4.1V under the same conditions as the primary charging, and then a vibration test was performed at 1000Hz for 1 hour while measuring the current value using a vibration tester. The presence or absence of short circuit occurrence due to this test is shown in the corresponding column of table 1.
TABLE 1
Figure BDA0002038333280000191
As is apparent from the results shown in table 1, in the batteries of samples 1 to 7 in which the dense structure portion having a porosity of less than 10% was formed at the position where the a/B was 0.8 or less by the thermal welding of the protruding portion of the separator sheet, short-circuiting of the positive and negative electrodes did not occur in the above vibration test. On the other hand, in the cell of sample 11, since the a/B of the portion where the dense structure portion was formed was 1 or more, a short circuit occurred 36 minutes after the start of the vibration test. It is thus recognized that the dense structure portion is preferably formed at a position having a < B.
Although specific examples of the present invention have been described in detail above, these are merely illustrative and do not limit the scope of the claims. The techniques described in the claims include various modifications and changes of the specific examples illustrated above. The all-solid-state battery disclosed herein is preferably used as a driving power source mounted in a vehicle such as an Electric Vehicle (EV), a Hybrid Vehicle (HV), or a plug-in hybrid vehicle (PHV).

Claims (3)

1. An all-solid battery includes a laminated electrode body having a laminated structure,
the laminated electrode body of the laminated structure has:
a positive electrode in which a positive electrode active material layer containing positive electrode active material particles and solid electrolyte particles is formed on a positive electrode current collector;
an anode in which an anode active material layer containing anode active material particles and solid electrolyte particles is formed on an anode current collector; and
a separator layer comprising a porous-structured substrate and solid electrolyte particles held in the substrate,
in at least a part of the end portions of the laminated electrode body, the negative electrode and the separator layer each have a protruding portion protruding further to the outside than an end portion of an opposing portion of the positive electrode and the negative electrode,
at least a part of the protruding portion of the separator layer is formed of a dense and dense structure to such an extent that contact between the positive electrode and the negative electrode is prevented,
the porous base material and the dense structural portion are made of a thermoplastic resin,
the dense and dense structure portion is formed by thermally fusing the protruding portion so that the three-dimensional mesh structure disappears,
here, when a shortest distance from an end of the facing portion of the positive and negative electrodes to the dense-structure portion is defined as a, and a shortest distance from a surface of the negative electrode active material layer at the end of the facing portion of the positive and negative electrodes to the positive electrode current collector at the end of the facing portion is defined as B, the dense-structure portion is formed at a position having a < B.
2. The all-solid battery according to claim 1, wherein the porosity of the porous substrate is at least 80%.
3. The all-solid battery according to claim 1 or 2,
the laminated electrode body is formed by laminating rectangular positive and negative electrodes and separator layers, and the dense structure portion is formed in a protruding portion of an end portion of each edge of the rectangular separator layer.
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